The production of tetraethyl orthosilicate (TEOS) from biomass provides a new way for TEOS production and biomass valorization. In this study, rice straw was treated using different fractionation methods, and the content, state, and reactivity of Si in the treated samples were investigated. It was found that acid treatment and ethanol extraction kept most Si in the biomass, while alkali treatment caused significant Si loss. Si was mainly present in the SiOx, Si−O−C, and Si−O−Si states in the surface of raw rice straw, cellulose and Klason lignin. The results showed that the Si−O−Si state in rice straw was beneficial for the formation of TEOS. The removal of lipids from rice straw facilitated the production of TEOS, giving the highest TEOS yield of 76.2 %. In contrast, the production of TEOS from other samples became difficult; the simultaneous conversion of the three organic components of rice straw also facilitated the production of TEOS.